Process for preparing layered organophosphorus inorganic polymers

ABSTRACT

Organophosphorus acid compounds react by a metathesis reaction in a liquid media with tetravalent metal ions to yield layered crystalline to amorphous inorganic polymers having the empirical formula M(O 3  PR) 2  where M is the tetravalent metal and R is an organic group convalently bonded to phosphorous. Typically, R can be bonded to phosphorus through carbon to form a phosphonate, or through oxygen to form a phosphate.

CROSS REFERENCE TO RELATED APPLICATION

This application is a Continuation-in-Part of U.S. Application Ser. No.945,971, filed on Sept. 26, 1978, and is related to Ser. No. 952,228filed Oct. 17, 1978, Ser. No. 966,197 filed Dec. 4, 1978, and Ser. No.7,275 abandoned filed Jan. 29, 1979. The disclosure of all of theseapplications is hereby incorporated herein by this reference.

BACKGROUND OF THE INVENTION

The present invention is directed to the preparation of solid inorganicpolymers having organo groups anchored to the surfaces of the polymers.The majority of the polymers formed are layered crystals which displayintercalation activity.

The interface surfaces of solids are responsive regions of chemical andphysical action. In many practical chemical and physical phenomena suchas absorption, corrosion inhibition, heterogeneous catalysis,lubrication, ion exchange activity, adhesion and wetting andelectrochemistry activity occurs as a consequence of the presence of adefinable solid surface. Solid agents are preferred in most processesover solution or homogeneously dispersed reactive alternatives primarilybecause they greatly simplify efficient separation of products fromreactants. However, solids invariably suffer from deficiencies inactivity and selectivity in the conversions they effect, due to inherentheterogeneity in their active sites which arises from the nature oftheir surface structure. Furthermore, much of the active sites areusually buried within the surface, and as a result of these two factors,elevated temperature and low conversions are typically encountered.Exceptions in which homogeneous catalysts are employed have been theMonsanto process for the production of acetic acid from methanol andcarbon monoxide employing rhodium, the production of linear alcoholsfrom olefins and syngas, ethylene oxidation by the Waker process,catalysis of olefins to form polymers, and other polymerization systems.

In an effort to achieve the best features of both homogeneous andheterogeneous processes, efforts have been made to chemically "anchor"known effective solution agents such as phosphines, nitriles,cyclopentadiene and the like, onto certain solids. Porous inorganicsurfaces and insoluble organic polymers have been employed. Silica hasbeen the inorganic of choice, the bonded ligand being attached byreaction with the --OH groups projecting from the surface. The organicpolymer most used has been polystyrene, with an appropriatemetal-coordinating function bonded via the phenyl rings. Results havebeen generally encouraging. However, there have been pervasive problemsderiving from the non-uniform situation of sites which has manifesteditself in loss of expected selectivity, activity and even in attrition.

Many inorganic solids crystallize with a layered structure and somecould present sites for anchoring active groups. In this form, sheets orslabs with a thickness of from one to more than seven atomic diameterslie upon one another. With reference to FIG. 1, strong ionic or covalentbonds characterize the intrasheet structure, while relatively weak vander Waals or hydrogen bonding occurs between the interlamellar basalsurfaces, in the direction perpendicular to their planes. Some of thebetter known examples are prototypal graphite, most clay minerals, andmany metal halides and sulfides. A useful characteristic of suchmaterials is the tendency to incorporate "guest" species in between thelamella.

In this process, designated "intercalation", the incoming guestmolecules, as illustrated in FIG. 2, cleave the layers apart and occupythe region between them. The layers are left virtually intact, since thecrystals simply swell in one dimension, i.e., perpendicular to thelayers. If the tendency to intercalate is great, then the host layeredcrystal can be thought of as possessing an internal "super surface" inaddition to its apparent surface. In fact, this potential surface willbe greater than the actual surface by a factor of the number of lamellacomposing the crystal. This value is typically on the order of 10² -10⁴.Although edge surface is practically insignificant compared to basalsurface, it is critical in the rate of intercalation, since theinclusion process always occurs via the edges. This is because bondingwithin the sheets is strong, and therefore, basal penetration of thesheets is an unlikely route into the crystal.

Previous studies of the intercalative behavior of layered compounds havemainly been conducted by solidstate chemists interested in the bulkeffects on the layered host materials. Graphite has, for example, beenextensively studied from an electronic point of view. In general, thefunction of the host is essentially passive. That is, on intercalationthe host serves as the matrix or surface with which the incoming guestmolecules interact, but throughout the process and on deintercalationthe guests undergo only minor perturbation.

In order for a more active process to occur during intercalation, suchas selective complexation or catalytic conversion, specific groups mustbe present which effect such activity. There might also be somepreferable geometric environment about each site, as well as someoptimal site-site spacing. These considerations have not beenextensively applied to intercalation chemistry simply because such kindsof active groups required are not found on layered surfaces.

An approach in which catalytically active agents have been intercalatedinto graphite or clays for subsequent conversions has been described in"Advanced Materials in Catalysis", Boersma, Academic Press, N.Y. (1977),Burton et al, editors, and "Catalysis in Organic Chemistry", Pinnavia,Academic Press, N.Y. (1977), G. V. Smith, editor, each incorporatedherein by reference. In neither case could it be shown that any activitywas occurring within the bulk of the solid. Rather, it is believed thatedge sites are responsible for the reactivity observed. In none of thecases was the active site covalently anchored, or fixed upon the lamellaof the host. Instead, the normal ionic or van der Waals forces ofintercalated guests were operating.

One of the few layered compounds which have potential available sites iszirconium phosphate Zr(O₃ POH)₂. It exists in both amorphous andcrystalline forms which are known to be layered. In the layeredstructure, the site-site placement on the internal surfaces is about 5.3A, which leads to an estimated 25 A² area per site. This area canaccommodate most of the functional groups desired to be attached to eachsite. The accepted structure, symbolized projection of a portion of alayer of this inorganic polymer and a representation of an edge view oftwo layers, are shown respectively in FIGS. 3, 4 and 5.

Besides the advantageous structural features of zirconium phosphate, thematerial is chemically and thermally stable, and non-toxic.

Quite a bit of work has been conducted on the zirconium phosphate,mainly because it has been found to be a promising inorganic cationexchanger for alkali, ammonium and actinide ions, Alberti, "Accounts ofChemistry Res." 11, 163, 1978, incorporated herein by reference. Inaddition, some limited work has been described on the reversibleintercalation behavior of layered zirconium phosphate toward alcohols,acetone, dimethylformamide and amines, Yamaka and Koizuma, "Clay andClay Minerals" 23, 477 (1975) and Michel and Weiss, "Z, Natur," 20, 1307(1965) both incorporated herein by reference. S. Yamaka described thereaction of this solid with ethylene oxide, which does not simplyincorporate between the layers as do the other organics, but rather wasfound to irreversibly react with the acidic hydroxyls to form a covalentbonded product, Yamaka, "Inorg. Chem." 15, 2811, (1976). This product iscomposed of a bilayer of anchored ethanolic groups aimed intointerlayers. The initial layer-layer repeat distance is expanded fromabout 7.5 A to 15 A, consistent with the double layer of organicspresent. The overall consequence of this reaction is to convertinorganic acid hydroxyls to bound organic alkanol groups. Thisconversion, while of interest, has limited if any improvement over thehydroxyls already available on zirconium phosphate.

Attempts have been made to add other moieties to zirconium phosphate.Results have only been successful with respect to exposed surfaces. Nopractical route was found to add them to the internal surfaces and sucha route is necessary if the full super surface of the crystals are to bemade utile.

SUMMARY OF THE INVENTION

According to the present invention there is provided a process for theproduction of inorganic polymers having organo groups covalently bondedto phosphorus atoms and in which the phosphorus atoms are, in turn,covalently bonded by an oxygen linkage to tetravalent metal atoms andwhen formed in a layered crystalline state provide the organo groups onall of the apparent and interlamellar surfaces.

The process of the invention comprises a liquid media reaction in whichat least one organophosphorus acid compound of the formula:

    [(HO).sub.2 OP].sub.n R

wherein n is 1 or 2 and R is an organo group covalently coupled to thephosphorus atom, and wherein when n is 2, R contains at least two carbonatoms and is directly or indirectly coupled to phosphorus atoms throughdifferent carbon atoms whereby the two phosphorus atoms are separated byat least two carbon atoms, is reacted with at least one tetravalentmetal ion selected from the group consisting of zirconium, cerium,thorium, uranium, lead and titanium, the molar ratio of phosphorus tothe tetravalent metal is 2 to 1. Reaction preferably occurs in thepresence of an excess of the phosphorus acid compound and the metal ionis provided as a compound soluble in the liquid media.

Where only one specie of an organophosphorus acid compound is providedas the reactant with the tetravalent metal compound, the end productwill have the empirical formula M(O₃ PR)₂. Phosphoric and/or phosphorousacid can also be present as reactive dilutants to form part of the solidinorganic polymeric structure which is the product of the reaction.

The products formed are layered crystalline to amorphous in nature. Forall products, the R groups may be directly useful or serve asintermediates for the addition of substitution of other functionalgroups. When the product is crystalline and n is 2, cross-linkingbetween the interlamellar layers occurs.

The normal liquid media is water. However, organic solvents,particularly ethanol, may be employed where water will interfere withthe desired reaction. Preferably, the solvent is the solvent in whichthe organophosphorus acid compound is prepared. Where theorganophosphorus acid compound has a sufficiently low melting point, itcan serve as the liquid media.

The metathesis reaction occurs at temperatures up to the boiling pointof the liquid media at the pressures involved, typically from ambient toabout 150° C. and more preferably from ambient to about 100° C. Whileformation of the solid inorganic polymer is almost instantaneous, thedegree of crystallinity of the product can be increased by refluxing thereaction products for times from about 5 to 15 hours. Crystallinity isalso improved by employing a sequestering agent for the tetravalentmetal ion.

THE DRAWINGS

FIG. 1 illustrates a layered microcrystal. Each lamellar slab is formedof strong covalent bonds and has a thickness of about 10 atoms.

FIG. 2 illustrates intercalation where the interlayer distance is shownas "d."

FIG. 3 illustrates the accepted structure for zirconium phosphate andspacing between layers. The dashed lines between zirconium (Zr) atoms isto establish the plane between them. In the drawing P=phosphorus,O=Oxygen and water of hydration is shown.

FIG. 4 illustrates a projection of zirconium plane showing acceptedspacing between Zr atoms and the available linkage area.

FIG. 5 is a symbolized depiction of spaced zirconium phosphate layersshowing covalently bonded hydroxyl groups and water of hydration.

FIG. 6 illustrates an exchange reaction between anchored groups "A" andgroups to be substituted for "B", and represents the portion of theorgano group linking the terminal group "A" or "B" to the crystals orthe organo-phosphorus acid compound reactant.

FIG. 7 is an x-ray powder diffraction pattern for semi-crystallinezirconium 2-carboxyethyl phosphonate as prepared in Example 1.

FIG. 8 is an x-ray powder diffraction pattern for highly crystallinezirconium 2-carboxyethyl phosphonate as prepared in Example 2.

FIG. 9 is infrared spectra for a mixed component product ZrO₃P(H)_(1/3), φ_(2/3))₂ as compared to the pure phases Zr(O₃ Pφ)₂ andZr(O₃ PH)₂ where φ is the radical --C₆ H₅.

FIG. 10 compares the loading of divalant metals on zirconium2-carboxyethyl phosphonate as a function of pH.

FIG. 11 compares the loading of Cu⁺² in the semi-crystalline reactionproduct of Example 1 to the highly crystalline product of Example 2.

FIG. 12 compares the loading of Cu⁺² on the reaction product of Example2 to thorium 2-carboxyethyl phosphonate.

FIG. 13 shows the rate of neutralization of zirconium 2-carboxyethylphosphonate by sodium hydroxide.

FIG. 14 shows the basic structural unit of the inorganic polymer formedby the process of the invention where n is 1 and where P=phosphorusatom, O=oxygen atom, M=tetravalent metal atom and R is the organo group.

FIG. 15 shows the basic structural unit of the inorganic polymer formedby the process of the invention where n is 2 and where P=phosphorusatom, O=oxygen atom, M=tetravalent metal atom and R is the organo group.

DETAILED DESCRIPTION

According to the present invention there is provided a process for theproduction of inorganic polymers in layered crystalline to amorphousstate by the liquid phase metathesis reaction of at least oneorganophosphorus acid compound having the formula:

    [(HO).sub.2 OP].sub.n R

wherein n is 1 or 2 and R is an organo group covalently coupled to thephosphorus atom with at least one tetravalent metal ion selected fromthe group consisting of zirconium, thorium, cerium, uranium, lead andtitanium to form a solid inorganic polymer precipitate in whichphosphorus is linked to the metal by oxygen and the organo group iscovalently bonded to the phosphorus atom. Where, in the organophosphoruscompound, n is 2, the end product occurs in the bis configuration. Inthis configuration, R must contain two or more carbon atoms, preferablyfrom two to about twenty carbon atoms, such that at least two carbonatoms separate the phosphorus atoms. In this bis configuration no singlecarbon atom is bound directly or indirectly to more than one [PO(OH)₂ ]group. When n is 1, and as depicted in FIG. 14, the organo groups willbe pendant from phosphorus atoms. When n is 2, and as depicted in FIG.15, cross-linking will occur between interlamellar surfaces of thecrystalline end product. Typically, the tetravalent metal ion isprovided as a soluble salt MX wherein M is as defined above and X is theanion(s) of the salt. Typical anions include halides, HSO₄ ⁻¹, SO₄ ⁻²,O₂ C-CH₃ ⁻¹, NO₃ ⁻¹, O⁻² and the like.

The majority of the polymeric reaction products formed are found to belayered crystalline or semi-crystalline in nature and, as such, providelayered structures similar to zirconium phosphates. The remainder areamorphous polymers possessing a large quantity of available pendantgroups similar to silica gel.

By the term "organophosphorus acid compound", as used herein, there ismeant a compound of the formula:

    [(HO).sub.2 OP].sub.n R

wherein n is 1 or 2, R is any group which will replace a hydroxyl ofphosphoric acid and/or the hydrogen of phosphorous acid and couple tothe acid by a covalent bond. Coupling to the acid may be through carbon,oxygen, silicon, sulfur, nitrogen and the like. Coupling through carbonor an oxygen-carbon group is presently preferred.

When, in the organophosphorus compound, n is 2, the end product occursin the bis configuration. In this configuration, R must contain two ormore carbon atoms, preferably from two to about twenty carbon atoms,such that at least two carbon atoms separate the phosphorus atoms. Inthis bis configuration, no single carbon atom is bound directly orindirectly to more than one [PO(OH)₂ ] group. Thus the groups which linkto the metal have the basic structural formula: ##STR1## wherein R" is abis group containing at least two carbon atoms bonded directly orindirectly to phosphorus and such that no phosphorus atoms are bondeddirectly or indirectly to the same carbon atom. The basic structures ofthe inorganic polymer forms are shown in FIGS. 14 and 15.

When coupling is through carbon, the organo phosphorus acid compound isan organo phosphonic acid and the product a phosphonate. When couplingis through oxygen-carbon, the organophosphorus acid compound is anorgano-phosphoric monoester acid and the product a phosphate.

The general reaction for phosphonic acids alone is shown in equation (1)below and for monoesters of phosphoric acid alone by equation (2).

    M.sup.+4 +2(HO).sub.2 OPR; M(O.sub.3 P-R).sub.2 +4H.sup.+  (1)

    M.sup.+4 +2(HO).sub.2 OP-OR'; M(O.sub.3 P-OR').sub.2 +4H.sup.+(2)

wherein R' is the remainder of the organo group.

The product contains phosphorus to metal in a molar ratio of about 2 to1, and the empirical formula for the product would show all groups boundto phosphorus.

While nowise limiting, the R groups attachable to phosphorus may besaturated and unsaturated, substituted and unsubstituted and include,among others, alkylene, alkyloxy, alkyne, aryl, haloalkyl, alkylaryl,aryloxy, mercaptoalkyl, aminoalkyl, carboxyalkyl, morpholinoalkyl,sulfoalkyl, phenoxyalkyl, beta-diketo alkyl, cyanoalkyl, cyanoalkoxy,and the like. In general, the organo group should occupy an area of nomore than about 25 A square for proper spacing. Larger groups may beemployed when mixed reagents are used.

The process for the formation of the novel inorganic polymers is ametathesis reaction conducted in the presence of a liquid mediumreceptive to the tetravalent metal ion at a temperature up to theboiling point of the liquid medium, preferably from ambient to about150° C. and, more preferably, to about 100° C. at the pressure employed.

While water is the preferred liquid medium, as most of theorganophosphorus acid compounds are hydroscopic, an organic solvent suchas ethanol may be employed, where water interferes with the reaction.There need only to be provided a solvent for the organophosphorus acidcompound since the tetravalent ion can be dispersed as a solid in thesolvent for slow release of the metal ion for reaction with theorganophosphorus acid compound. If it has a sufficiently low meltingpoint, the organophosphorus acid compound may serve as a solvent.Typically, the liquid medium is the liquid medium in which theorganophosphorus acid is formed.

For complete consumption of the tetravalent compound, the amount of acidemployed should be sufficient to provide two moles of phosphorus permole of tetravalent metal. An excess is preferred. Phosphorous acidand/or phosphoric acid, if present, will enter into the reaction andprovide an inorganic polymer diluted in respect of the organo group inproportion to the amount of phosphorous or phosphoric acid employed.

Reaction is virtually instantaneous at all temperatures leading toprecipitation of layered crystalline, semi-crystalline or amorphousinorganic polymer solid.

The amorphous phase appears as a gel similar to silica gel. The gel canbe crystallized by extended reflux in the reaction medium, usually fromabout 5 to about 15 hours. The semi-crystalline product is characterizedby a rather broad x-ray powder pattern. (See FIGS. 7 and 8.)

The presence of sequestering agents for the metal ion slows down thereaction and also leads to more highly crystalline products. Forinstance, a semi-crystalline solid was prepared by the aqueous phasereaction of zirconium chloride and excess 2-carboxyethyl phosphonicacid, followed by 15 hours of reflux. A highly crystalline modificationwas prepared under identical conditions except that hydrogen fluoridewas added to the reaction mixture. A slow purge of N₂ over the surfaceof the reaction solution slowly removed the fluoride from the system.Fluoride is a very strong complexing agent for zirconium ions. The slowremoval of fluoride results in slow release of the metal ion forreaction with the phosphonic acid, resulting in an increase incrystallinity.

A similar enhancement of crystallinity was obtained in the reaction ofthorium nitrate with 2-carboxyethyl phosphonic acid. Nitrate ion is asequestering agent for thorium and the rate of formation of this productis slow and the product polymer quite crystalline.

As compared to zirconium phosphate forming crystals of 1-5 microns, thecrystals of 100 to greater than 1000 micron in size have been preparedin accordance with the invention.

A property critical for many of the likely uses of the products is theirthermal stability. This is because deficiencies in activity can becompensated for by reasonable increases in operating temperature. Astandard method for thermal characterization is thermalgravimetric/differential thermal analysis (TGA/DTA). These techniquesindicate changes in weight and heat flow of substances as a function oftemperature. Thus, decomposition and phase changes can be monitored astemperature increases.

Zirconium phosphate itself is quite a stable material. Interlayer wateris lost at about 100° C., and a second dehydration involving thephosphates occurs above 400° C. The practical ion-exchanging abilitiesare lost in this step.

The inorganic polymers of this invention are also stabilized towardthermal decomposition as compared to pure organic analogs as a result ofthe fixation and separating effect of the inorganic support.

For zirconium chloromethyl phosphonate, for instance, weight loss didnot commence until well above 400° C. The organic fragment was half lostat about 525° C., indicating remarkable stability. Decomposition ofzirconium 2-carboxyethylphosphonate begins between 300° and 400° C. Thedecomposition process inflection point, approximate midpoint, falls atabout 400° C.

While not bound by theory, phosphates probably decompose like carboxylicesters to yield acid and unsaturates, whereas phosphonates likely formradicals by homolytic cleavage. Both nitrophenyl and cyanoethylphosphates of zirconium decompose at about 300° C. The phenylphosphonatedecomposes at about 425° C.

Besides proving the suitability of such compounds in elevatedtemperature applications, the TGA analysis affirmed covalent bonding tophosphorous. This is because normal intercalative interactions arereversed within 10°-100° C. above the boiling point of the guest.

The process of this invention permits a wide variety of inorganicpolymers to be formed having the characteristic of the organo groupprotected by the inorganic polymer structure and with subsequentexchange or substitution reactions, the formation of other inorganicpolymers. Polymers formed may be block, random and the like.

For instance, a mixture of phenyl phosphonic acid and phosphorous acidwas simultaneously reacted with zirconium ion to yield a single solidphase. The interlamellar distance was the same as zirconium phenylphosphonate, or about 15.7 A. There was no reflection at 5.6 A, thenormal spacing for zirconium phosphite. This established that thelargest group should determine interlamellar distance and indicated thata discreet zirconium phosphate phase was not present. Evidence of achange in chemical environment of P-H band was established by infraredanalysis. In infrared analysis of zirconium phosphite, P-H stretching isobserved as a sharp band at 2740 cm⁻¹ (moderate intensity). In the mixedcompound solid, this band was shifted to 2440 cm⁻¹ and broadened.

Another route is to exchange one pendant group for another. The exchangereaction is described in Example 31. While not bound by theory, thepresent expected points of exchange are at the periphery of the crystaland are schematically illustrated in FIG. 6. Such bifunctional materialsexhibit the quality of providing terminal groups for attracting speciesfor intercalation and then interaction with the internal groups.

The reaction of bis acids with tetravalent metal ions permitsinterlamellar cross-linking by a reaction such as (HO)₂ OPCH₂ CH₂OP(OH)₂ +M⁺⁴ → CH₂ CH₂ where as in FIG. 6, represents the interlamallarlayers to which the alkyl group is anchored. As with all organo groups,for the bis configuration at least two carbon atoms are present,preferably from two to twenty atoms, and the phosphorus atoms are linkeddirectly or indirectly to different carbon atoms. Since size of thelinking group will control and fix interlamellar spacing, there isprovided effective laminar sieves of fixed spacing for applicationanalogous to that of molecular sieves.

Ion exchange activity was established with pendant carboxylic acidgroups. Prepared zirconium 2-carboxyethyl phosphonate was established tointerlayer distance of 12.8 A. When intercalated to form itsn-hexylammonium salt interlayer distance increased to 27.2 A. Whensodium was taken up, layer spacing increased to 14.2 A. X-ray andinfrared data indicated the highly crystalline inorganic polymer tobehave as expected for carboxylic acid with behavior analogous to ionexchange resins except that both external and internal surfaces werefunctional establishing them as super surface ion exchange resins.Moreover, since the inorganic polymers can be prepared asmicrocrystalline powders, diffusion distances are short.

As summarized in Table 1, nitrile and mercapto anchored groups show theability to take up silver and copper ions at room temperature forcatalytic activity.

                  TABLE 1                                                         ______________________________________                                                                Loading MMole Metal                                   Anchored Group                                                                            Metal Ion   MMole Zr                                              ______________________________________                                        --O˜CN                                                                              0.1 M Ag+   0.20                                                    ˜SH 0.1 M Ag+   1.0                                                   --O˜CN                                                                              0.1 M Cu ++ 0.10                                                  --O˜CN                                                                              0.1 M Cu++  0.10                                                              0.5 M HOAc                                                                    0.5 M NaAc                                                        ______________________________________                                         ˜ = groups formed of carbon and hydrogen.                               Ac = acetate radical                                                     

The alternate to catalytic utility is to attach the metals to theorganophosphorus acid prior to reaction with the soluble tetravalentmetal compound.

The high surface area of the crystalline products also make them utilefor sorption of impurities from aqueous and non-aqueous media.

Another utility is as an additive to polymeric compositions. Similar tothe high aspect ratio provided by solids such as mica which improve thestress strain properties of the polymers, the powdered inorganic polymerproducts of the invention can serve the same function and add features.By the presence of reactive end groups on the bonded organo groups,chemical grafting to the polymer network can be achieved to increasecomposite crystallinity and elevating heat distortion temperature. Inaddition, the presence of phosphorus induces flame retardant properties,as would bound halogen.

Still other utilities include solid lubricants which behave like mica,graphite and molybdenum disulfide; solid slow release agents whereintercalated materials can be slowly leached or released from theinternal layers of the crystals; substance displaying, electrical,optical phase or field changes with or without doping and the like.

While nowise limiting, the following Examples are illustrative of thepreparation of solid inorganic polymers of this invention and some oftheir utilities.

In the Examples conducted in the atmosphere no extraordinary precautionswere taken concerning oxygen or moisture. Reagents were usually used asreceived from suppliers. The products formed are insoluble in normalsolvents and do not sublime. However, the combined weight of yield data,spectroscopy, elemental analyses, TGA and powder diffraction resultsconfirm the compositions reported with good reliability.

X-ray powder patterns were run on a Phillips diffractometer using CuKradiation.

Thermal analyses were conducted on a Mettler instrument. Infraredspectra were obtained with a Beckmann Acculab spectrophotometer.

Surface area were determined using both a dynamic flow method, on aQuantasorb instrument, and also with a vacuum static system on aMicromeritic device. Both employ a standard BET interpretation ofnitrogen coverage.

Titrations were carried out in aqueous or alcoholic medium. A standardcombination electrode and an Orion Ionalyzer pH meter were used for pHdetermination. The titration of the solid interlamellar anchoredmaterials is analogous to the titration of an ion exchange resin.

EXAMPLE 1

To a 250 ml 3-necked flash fitted with a reflux condenser, stirrer,thermometer and heating mantle, there was charged 21.8 ml of a 38%aqueous solution providing 11.1 g of 2-carboxyethylphosphonic acid in 25ml of water. Stirring was commenced at room temperature and 9.2 grams ofZrOCl₂ in 10 ml of water was added. A white precipitate was immediatelyformed. Water (17 ml) was added to fluidize the solids and temperatureraised to about 90° to about 100° C. to gentle reflux which wascontinued for 15 hours. The slurry was cooled to room temperature andthe white solid isolated by filtration. The solid was washed on thefilter with water, acetone, then ether. The solid product was dried to aconstant weight of 12.1 grams determined to be semi-crystalline and tohave the empirical formula Zr(O₃ PCH₂ CH₂ COOH)₂. The x-ray powderdiffraction pattern is shown in FIG. 7.

EXAMPLE 2

The procedure of Example 1 repeated except that 4 ml of a 48% aqueoussolution of hydrogen fluoride was added to the initial mixture andslowly removed by a slow purge of nitrogen maintained during reflux. Theobserved to calculated atomic composition was as follows:

    ______________________________________                                        Atom       Observed       Calculated                                          ______________________________________                                        C          18.4%          18.23%                                              H          2.84%          2.54%                                               P          15.5%          15.7%                                               ______________________________________                                    

The x-ray diffraction pattern for the highly crystalline product isshown in FIG. 8. Interlayer spacing was determined to be 12.8 A.

EXAMPLE 3

Using the procedure of Example 1, there was reacted 46 grams ofchloromethylphosphonic acid and 5.5 grams of ZrOCl₂.8H₂ O to yield 5.9grams of a crystalline solid having the empirical formula Zr(O₃ PCH₂Cl)₂ with an interlayer spacing of 10.5 A.

EXAMPLE 4

Example 3 was repeated except that 10 grams of chloromethylphosphonicacid was reacted with 6.6 grams of Th(NO₃)₄.4H₂ O to yield 6.0 grams ofcrystalline solid having the empirical formula Th(O₃ PCH₂ Cl)₂ with aninterlayer spacing of 10.5 A.

EXAMPLE 5

Example 4 was repeated except that 12.2 grams of chloromethylphosphonicacid was reacted with 3.9 grams of PbO₂ to yield 5.1 grams of acrystalline solid having the empirical formula Pb(O₃ PCH₂ Cl)₂ with aninterlayer spacing of 9.83 A.

EXAMPLE 6

Example 4 was repeated except that 0.55 gram of chloromethylphosphonicacid was reacted with 0.34 gram of UCl₄ to yield 0.4 gram of acrystalline solid having the empirical formula U(O₃ PCH₂ Cl)₂ with aninterlayer spacing of 10.0 A.

EXAMPLE 7

Example 4 was repeated except that 4.74 grams of chloromethylphosphonicacid was reacted with 4.4 grams of titanium tetrachloride to yield 5.9grams of a crystalline solid having the empirical formula Ti(O₃ PCH₂Cl)₂ with an interlayer spacing of 10.4 A.

EXAMPLE 8

Using the procedure of Example 1, there was reacted 1.99 grams ofphenylphosphonic acid with 1.96 grams of ZrOCl₂.8H₂ O to yield 2.56grams of a crystalline solid having the empirical formula Zr(O₃ PC₆ H₅)₂with an interlayer spacing of 14.9 A. Dynamic surface area was 186 m² /gand static surface area was 220 m² /g.

EXAMPLE 9

Example 8 was repeated except that 2.03 grams of phenylphosphonic acidwas reacted with 3.48 grams of Th(NO₃)₄.4H₂ O to yield 3.44 grams of acrystalline solid having the empirical formula Th(O₃ PC₆ H₅)₂ with aninterlayer spacing of 14.7 A. Dynamic and static surface areas were ineach instance 67 m² /g.

EXAMPLE 10

Example 8 was repeated except that 0.9 gram of phenylphosphonic acid wasreacted with 0.7 gram of Ce(HSO₄) to yield 1.3 grams of a crystallinesolid having the empirical formula Ce(O₃ PC₆ H₅)₂ with an interlayerspacing of 15.5 A.

EXAMPLE 11

Example 8 was repeated except that 1.67 grams of phenylphosphonic acidwas reacted with 1.0 grams of titanium tetrachloride. There was formed1.94 grams of a crystalline solid of the empirical formula Ti(O₃ PC₆H₅)₂ with an interlayer spacing of 15.2 A. Dynamic surface area was 151m² /g and static surface area was 167 m² /g.

EXAMPLE 12

As in Example 1, there was reacted about 10 grams ofmercaptomethylphosphonic acid with 6.3 grams of ZrOCl₂.8H₂ O to yield7.3 grams of an amorphous solid having the empirical formla Zr(O₃ PCH₂SH)₂.

EXAMPLE 13

As in Example 1, there was reacted 2.0 grams of2-mercaptoethylphosphonic acid with 1.0 gram of ZrOCl₂ to yield 1.72grams of a crystalline solid having the empirical formula Zr(O₃ PCH₂ CH₂SH)₂ and with an interlayer spacing of 15.5 A.

EXAMPLE 14

As in Example 1, there was reacted 0.50 gram of 2-aminoethylphosphonicacid with 0.64 grams of ZrOCl₂.8H₂ O to yield 0.82 gram of a crystallinesolid having the empirical formula Zr(O₃ PCH₂ CH₂ NH₂)₂.

EXAMPLE 15

As in Example 1, there was reacted 1.9 grams of 2-carboxyethylphosphonicacid with 2.3 grams of Th(NO₃)₄.4H₂ O to yield 1.97 grams of acrystalline solid having the empirical formula Th(O₃ PCH₂ CH₂ COOH)₂with an interlayer spacing of 14.2 A.

EXAMPLE 16

As in Example 1, there was reacted 16.1 grams of2-carboxymethylphosphonic acid with 13.5 grams of ZrOCl₂.8H₂ O to yield15.3 grams of a crystalline solid having the empirical formula Zr(O₃PCH₂ COOH)₂ with an interlayer spacing of 11.1 A.

EXAMPLE 17

The procedure of Example 1 was repeated except there was reacted 5.64grams of morpholinomethylphosphonic acid in ethanol with 5.0 grams ofZrOCl₂.8H₂ O to yield 6.1 grams of a crystalline solid having theempirical formula Zr(O₃ PCH₂ NCH₂ CH₂ OCH₂ CH₂)₂ with an interlayerspacing of 16 A.

EXAMPLE 18

Following the procedure of Example 1, there was reacted 7.4 grams of2-sulfoethylphosphonic acid with 5.0 grams of ZrOCl₂.8H₂ O to yield 6.1grams of an amorphous solid having the empirical formula Zr(O₃ PCH₂ CH₂SO₃ H)₂.

EXAMPLE 19

As in Example 1, 13.3 grams of ethylene bisphosphonic acid was reactedwith 5.6 grams of ZrOCl₂.8H₂ O to yield 3.7 grams of crystallineinorganic polymeric solid having ethylene units bridging P atoms of theadjacent lamina with an interlayer spacing of 6.92 A.

EXAMPLE 20

As in Example 1, 4.9 grams of phenoxymethylphosphonic acid was reactedwith 3.7 grams of ZrOCl₂.8H₂ O to yield 4.3 grams of a crystalline solidhaving the empirical formula Zr(O₃ PCH₂ OC₆ H₅)₂ with an interlayerspacing of 18 A.

EXAMPLE 21

As in Example 1, 2.0 grams of a phosphonic acid of the formula ##STR2##was reacted with 0.93 gram of ZrOCl₂ to yield 1.87 grams of acrystalline solid of the empirical formula ##STR3## with an interlayerspacing of 11.3 A.

EXAMPLE 22

As in Example 1, 9.45 grams of 2-bromoethyl phosphonic acid was reactedwith 6.2 grams of ZrOCl₂.8H₂ O to yield 8.5 grams of a solid having theempirical formula Zr(O₃ PCH₂ CH₂ Br)₂ and a layer spacing of 13 A.

EXAMPLE 23

As in Example 1, there was reacted 6.3 grams of (HO)₂ OP-OCH₂ CH₂ CNadded as BaO₃ POCH₂ CH₂ CN.2H₂ O in aqueous HCl with 1.1 grams ofZrOCH₂.8H₂ O to yield 1.35 grams of a solid having the empirical formulaZr(O₃ POCH₂ CH₂ CN)₂ with an interlayer spacing of 13.2 A.

EXAMPLE 24

As in Example 1, there was reacted 4.6 grams of (HO)₂ OPCH₂ CN added towater as the diethyl ester and hydrolyzed in situ to the acid with 4.3grams of ZrOCl₂.8H₂ O to form 4.6 grams of a crystalline precipitatehaving the empirical formula Zr(O₃ PCH₂ CN)₂.

EXAMPLE 25

As in Example 1, there was reacted 3.15 grams of (HO)₂ OPOC₆ H₄ NO₂added as the sodium salt in hydrochloric and with 1.32 grams ofZrOCl₂.8H₂ O to yield 1.66 grams of a crystalline precipitate having theempirical formula Zr(O₃ POC₆ H₄ NO₂)₂ with an interlayer spacing of 15.8A.

EXAMPLE 26

Example 25 was repeated except the amount of the phosphoric acid esterwas reduced to 3.03 grams and reacted with 2.21 grams of Th(NO₃)₄.4H₂ Oto yield 1.66 grams of a crystalline precipitate having the empiricalformula Th(O₃ POC₆ H₄ NO₂)₂ with an interlayer spacing of 16.4 A.

EXAMPLE 27

Phosphorous acid, phenyl phosphonic acid and a zirconium salt werereacted in a molar ratio of 2:4:3 to yield a crystalline solid havingthe empirical formula Zr[O₃ P(H)_(1/3) (C₆ H₅)_(2/3) ]₂ having aninterlayer distance of 15.7 A. The infrared spectra of this product iscompared to the infrared spectra for Zr(O₃ PH)₂ and Zr(O₃ PC₆ H₅)₂ inFIG. 9.

EXAMPLE 28

Diethyl 2-carboethoxyethyl phosphonate was prepared by the Arbuzovreaction of triethyl phosphite and ethyl 3-bromopropionate. Thephosphonate ester product was hydrolyzed to the acid in refluxing HBrand then reacted in situ with zirconium ion. The resultant layeredcompound, zirconium 2-carboxyethyl phosphonate, has interlamellarcarboxylic acid substituents. The highly crystalline modification had aninterlayer distance of 12.8 A and its n-hexylammonium salt wasdetermined to have interlayer distance of 27.2 A. Thorium 2-carboxyethylphosphonate was also prepared in an analogous manner.

The interlamellar carboxylic acid was determined to be a strong carbonylstretching frequency at 1710 cm⁻¹. Upon sodium salt formation thisshifts to 1575 and 1465 cm-1. The x-ray powder pattern of the sodiumsalt indicates a layer spacing of 14.2 A. The x-ray and infrared data ofthe interlamellar carboxylic acid and its salts indicate that thismaterial behaves as a carboxylic acid. This infrared behavior isanalogous to that of ion exchange resins with carboxylic functionality.

The ion exchange behavior of the interlamellar carboxylic acid wasinvestigated with a number of metals. FIG. 10 represents the pH vs.loading profile for the 2H⁺ -M⁺² exchange of Cu⁺², Ni⁺², and Co⁺² withsemicrystalline zirconium 2-carboxyethyl phosphonate. These profiles arein the normal pH range for the exchange of these metals with carboxylicacids.

The influence of crystallinity of the H⁺ -Cu⁺² exchange equilibrium isdemonstrated in FIG. 11. The pH₀.5 is about 3.8 for the semi-crystallineand about 4.5 for the highly crystalline. This indicates that the matrixsupporting the anchored functional group influences the reactivity ofthe functional group.

The interlamellar metal ion also has an influence on the H⁺ /Cu⁺²exchange equilibrium. High crystallinity modifications of thorium andzirconium 2-carboxyethylphosphonate were compared. This data ispresented in FIG. 12. The thorium compound is the stronger acid by about0.3 pKa units in this reaction (pH₀.5 =4.2 vs 4.5).

EXAMPLE 29

The reaction rate of zirconium 2-carboxyethylphosphonate with aqueoussodium hydroxide was determined by its addition to an aqueous solutionof NaOH with decrease in pH measured as a function of time. As shown inFIG. 13, the concentration of hydroxide ion changed by over three ordersof magnitude in 15 seconds representing reaction of 80% of thecarboxylic groups. This established that the interlamellar reaction wasquite facile and diffusion into the crystal did not involve a highkinetic barrier. Prolonged exposure at a pH of about 9 to 10 or higher,however, resulted in hydrolysis of the crystal with formation of ZrO₂.

EXAMPLE 30

Titanium phenylphosphonate having a surface area of about 151-167 m² /gwas evaluated as sorption solid. A sample of water was contaminated with1-hexanol (1700 ppm), chloroform (1100 ppm) and benzene (300 ppm). Onehundred ml of this solution was treated with 2.4 g of the titaniumphenylphoshonate. Analysis established that the solid absorbed theorganics. The distribution co-efficients were 750 (benzene), 430(1-hexanol) and 250 (CHCl₃). Absorption of benzene was preferred.

EXAMPLE 31

Solid zirconium 2-bromoethyl phosphonate was slurried in an aqueoussolution of 2-carboxyethyl phosphonic acid. A trace (1% mol) of HF wasadded and the mixture refluxed overnight. The infrared spectrum of thesolid after this period definitely showed the presence of the carboxylicacid carbonyl band at 1710 cm⁻¹. The x-ray powder pattern of theexchanged product was virtually identical to the starting material. Thiswas likely due to the fact that zirconium 2-bromoethyl phosphonate hasan interlayer spacing of 13.0 A and the 2-carboxy analog 12.8 A. Basedon stoichiometry, about 5 to 10% of the sites were exchanged. This beingmore than the apparent surface site, interlamellar exchange took place.

EXAMPLE 32

As in Example 1, 14 g of 3-sulfopropylphosphonic acid (prepared by theaddition of diethylphosphite to propane sulfone followed by hydrolysis)was added 9 g of ZrOCl₂.8H₂ O yielding 10.1 g of a solid having theformula Zr(O₃ PCH₂ CH₂ CH₂ SO₃ H)₂ and a d-spacing of 18.8 A.

EXAMPLE 33

In the following table are listed other compounds which have beenprepared by the method given in Example 1.

    __________________________________________________________________________    Compound Produced                                                                            Phosphonic Acid Used                                                                          M.sup.+4 Salt Used                                                                     Wt. Product                           __________________________________________________________________________    ZR(O.sub.3 PCH.sub.2 CH.sub.2 CH.sub.2 PO.sub.3).sub.1                                       0.79g H.sub.2 O.sub.3 PCH.sub.2 CH.sub.2 CH.sub.2 PO.sub.3                    H.sub.2         0.68g ZrOCl.sub.2                                                                      1.05                                  ZR(O.sub.3 PCH.sub.2 CH.sub.2 CH.sub.2 PO.sub.3 H.sub.2).sub.2                               0.79g H.sub.2 O.sub.3 PCH.sub.2 CH.sub.2 CH.sub.2 PO.sub.3                    H.sub.2         0.34g ZrOCl.sub.2                                                                      0.45g                                 Ti.sub.1/2 Th.sub.1/2 (O.sub.3 P--C.sub.6 H.sub.5).sub.2                                     1.17g H.sub.2 O.sub.3 P--C.sub.6 H.sub.5                                                      1.66g 30% TiOCl.sub.2                                                                  2.35g                                                                2.05g Th(NO.sub.3).sub.4                       Th(O.sub.3 P--CH.sub.3).sub.2                                                                0.845g H.sub.2 O.sub.3 P--CH.sub.3                                                            2.25g Th(NO.sub.3).sub.4                                                               1.7g                                  Zr(O.sub. 3 P--CH.sub.3).sub.2                                                               0.814g H.sub.2 O.sub.3 PCH.sub.3                                                              0.75g ZrOCl.sub.2                                                                      0.87g                                 Th(O.sub.3 PCH.sub.2 OH).sub.2                                                               0.522g H.sub.2 O.sub.3 PCH.sub.2 OH                                                           1.35 Th(NO.sub.3).sub.4                                                                1.12g                                 Th(O.sub.3 P--C.sub.18 H.sub.37).sub.2                                                       0.95g (CH.sub.3 O).sub.2 OPC.sub. 18 H.sub.37                                                 0.76g Th(NO.sub.3).sub.4                                                               1.1g                                  Ti(O.sub.3 P--C.sub.6 H.sub.4 --OCH.sub.3).sub.2                                             0.98g H.sub.2 O.sub.3 P--C.sub.6 H.sub.4 OCH.sub.3                                            1.17g 30% TiOCl.sub.2                                                                  0.9g                                  U(O.sub.3 P--C.sub.6 H.sub.5).sub.2                                                          1.29g H.sub.2 O.sub.3 P--C.sub.6 H.sub.5                                                      1.55g UCl.sub.4                                                                        2.04g                                 Zr[(O.sub.3 P(CH.sub.2).sub.3 CO.sub.2 H].sub.2                                              51.9g H.sub.2 O.sub.3 P(CH.sub.2).sub.3 CO.sub.2 H                                            49.7g ZrOCl.sub.2                                                                      56.7g                                 Zr[O.sub.3 P(CH.sub.2).sub.4 CO.sub.2 H].sub.2                                               25.5g H.sub.2 O.sub.3 P(CH.sub.2).sub.4 CO.sub.2 H                                            22.6g ZROCl.sub.2                                                                      25.3g                                 Zr(O.sub.3 PCH═CH.sub.2).sub.2                                                           12.0g Na.sub.2 O.sub.3 PCH═CH.sub.2                                                       23.9g ZrOCl.sub.2                                                                      11.6g                                 Ti(O.sub.3 PCH═CH.sub.2).sub.2                                                           9.44g Na.sub.2 O.sub.3 PCH═CH.sub.2                                                       16.3g TiCl.sub.4                                                                       7.1g                                  Th(O.sub.3 PCH═CH.sub.2).sub.2                                                           10.6g Na.sub.2 O.sub.3 PCH═CH.sub.2                                                       21.0g Th(NO.sub.3).sub.4                                                               7.9g                                  __________________________________________________________________________

EXAMPLE 34

In the following table are listed the sources of the intermediatephosphonic acid or monoester phosphoric acids for the preceedingexamples.

    __________________________________________________________________________    Intermediate    Example No.                                                                           Source                                                __________________________________________________________________________    H.sub.2 O.sub.3 PCH.sub.2 CH.sub.2 CO.sub.2 H                                                 1, 2, 15                                                                              Hydrolysis of Triethylester                                                   (McConnell et al, JACS, 78, 4453 (1956))              H.sub.2 O.sub.3 PCH.sub.2 Cl                                                                  3, 4, 5, 6, 7                                                                         Supplied by PCR, Inc.                                 H.sub.2 O.sub.3 P-C.sub.6 H.sub.5                                                             8, 9, 10, 11, 33                                                                      Supplied by AldrichChemicals.                         H.sub.2 O.sub.3 PCH.sub.2 SH                                                                  12      (C.sub.2 H.sub.5 O).sub.2 OPCH.sub.2 Cl +                                     Thiourea reaction                                                             followed by hydrolysis.                               H.sub.2 O.sub.3 PCH.sub.2 CH.sub.2 SH                                                         13      (C.sub.2 H.sub.5 O).sub.2 OPCH═CH.sub.2 +                                 CH.sub.3 COSH followed                                                        by hydrolysis.                                        H.sub.2 O.sub.3 PCH.sub.2 CH.sub.2 NH.sub.2                                                   14      Purchased from Calbiochem-Behring Corp.               H.sub.2 O.sub.3 PCH.sub.2 CO.sub.2 H                                                          16      Hydrolysis of Triethylester Supplied                                          by Aldrich.                                            ##STR4##        17      Field, JACS, 74, 1528 (1952).                        H.sub.2 O.sub.3 PCH.sub.2 CH.sub.2 SO.sub.3 H                                                 18      Arbuzov reaction of (C.sub.2 H.sub.5 O).sub.3 P                               with                                                                          NaSO.sub.3 C.sub.2 H.sub.4 Br followed by                                     hydrolysis.                                           H.sub.2 O.sub.3 PCH.sub.2 CH.sub.2 PO.sub.3 H.sub.2                                           19      Arbuzov reaction of (C.sub.2 H.sub.5 O).sub.3 P                               with                                                                          BrCH.sub.2 CH.sub.2 Br followed by hydrolysis.        H.sub.2 O.sub.3 P-CH.sub.2 OC.sub.6 H.sub.5                                                   20      Walsh et al, JACS, 78, 4455 (1956)                     ##STR5##        21      Reaction of Na acetylacetonate with                                          (C.sub.2 H.sub.5 O).sub.2 OPCH.sub.2 CH.sub.2 Br                              followed by hydrolysis.                               H.sub.2 O.sub.3 PCH.sub.2 CH.sub.2 Br                                                         22      Hydrolysis of diethylester supplied                                           by Aldrich.                                           H.sub.2 O.sub.3 POCH.sub.2 CH.sub.2 CN                                                        23      Hydrolysis of Ba.sup.+2 salt supplied                                         by Aldrich.                                           H.sub.2 O.sub.3 PCH.sub.2 CN                                                                  24      Hydrolysis of diethylester supplied                                           by Aldrich.                                           H.sub.2 O.sub.3 POC.sub.6 H.sub.4 NO.sub.2                                                    25, 26  Hydrolysis of sodium salt supplied                                            by Aldrich.                                           H.sub.2 O.sub.3 P(CH.sub.2).sub.3 SO.sub.3 H                                                  32      Addition of (C.sub.2 H.sub.5 O).sub.2 PONa to                                 propane                                                                       sulfone followed by hydrolysis.                       H.sub.2 O.sub.3 P(CH.sub.2).sub.n CO.sub.2 H                                                  33      Arbuzov reaction of (C.sub.2 H.sub.5 O).sub.3 P                               and                                                   n = 3,4                 hydrolysis.                                                                   hydrolysis.                                           H.sub.2 O.sub.3 PCH = CH.sub.2                                                                33      Hydrolysis of ester supplied                                                  by Aldrich.                                           H.sub.2 O.sub.3 P-C.sub.6 H.sub.4 OCH                                                         33      Purchased from Alfa Imorg.                            H.sub.2 O.sub.3 PC.sub.18 H.sub.37                                                            33      Hydrolysis of dimethylester purchased                                         from Alfa.                                            H.sub.2 O.sub.3 PCH.sub.2 OH                                                                  33      Purchased from Alfa.                                  H.sub.2 O.sub.3 PCH.sub.3                                                                     33      Purchased from Alfa.                                  H.sub.2 O.sub.3 P(CH.sub.2).sub.3 PO.sub.3 H                                                  33      Purchased from Alfa.                                  __________________________________________________________________________

EXAMPLE 35

Using a Quantasorb surface area analyzer and pycnometer, the followingmeasurements were made:

    ______________________________________                                        Compound        Density     Surface Area                                      ______________________________________                                        Ti(O.sub.3 PC.sub.6 H.sub.5).sub.2                                                            1.642 g/cc  151.5 m.sup.2 /g                                  Zr(O.sub.3 PC.sub.6 H.sub.5).sub.2                                                            1.828 g/cc  185.9 m.sup.2 /g                                  Zr(O.sub.3 PCH.sub.2 CH.sub.2 PO.sub.3)                                                       2.400 g/cc  55.12 m.sup.2 /g                                  Zr(O.sub.3 PCH.sub.2 CH.sub.2 CO.sub.2 H).sub.2                                               2.090 g/cc  26.15 m.sup.2 /g                                  Th(O.sub.3 PC.sub.6 H.sub.5 Z).sub.2                                                          2.519 g/cc  66.9 m.sup.2 /g                                   Th(O.sub.3 PCH.sub.2 Cl).sub.2                                                                3.284 g/cc   9.73 m.sup.2 /g                                  ______________________________________                                    

These data demonstrate the high surface area of the products prepared,and also the densities verify a common structure.

EXAMPLE 36

Using the method outlined in Example 1, the following compounds areprepared:

    ______________________________________                                         1. M[O.sub.3 P(CH.sub.2).sub.nPR.sub.2 ].sub.2 ;                                                   M = Ti.sup.+4, Zr.sup.+4,                                                     Hf.sup.+4, U.sup.+4, Th.sup.+4,                                               Ce.sup.+4, Pb.sup.+4 ;                                                        n = 1-10;                                                                     R = CH.sub.3,                                                                 C.sub.2 H.sub.5, C.sub.6 H.sub.5.                        2. M[O.sub.3 P(CH.sub.2).sub.nOP(OR).sub.2 ].sub.2 ;                                               M, n, R as above.                                       3. M[O.sub.3 P(CH.sub.2).sub.n.sup.+N(CH.sub.3).sub.3 X.sup.- ].sub.2                               M, n, as above; X =                                                           halide, sulfate                                                               nitrate, phosphate,                                                           acetate.                                                 4. M[O.sub.3 P(CH.sub.2).sub.nNHCS.sub.2 H].sub.2 ;                                                M, n, as above.                                          5. M[O.sub.3 P(CH.sub.2).sub.nN(CH.sub.2 CO.sub.2 H).sub.2 ].sub.2                                 M, n, as above.                                         6. M[O.sub.3 P(CH.sub.2).sub.n  .sup.+NH.sub.2(CH.sub.2).sub.3 SO.sub.3.su    p.- ].sub.2 ;         M, n, as above.                                          7. M[O.sub.3 P(CH.sub.2).sub.nNC].sub.2 ;                                                          M, n, as above.                                          8. M[O.sub.3 P(CH.sub.2).sub.nCCH].sub.2 ;                                                         M, n, as above.                                          ##STR6##             M as above.                                              ##STR7##             M, n, as above.                                         11. M[O.sub.3 P(CH.sub.2).sub.nSR].sub.2 ;                                                          M, n, as above;                                                               R = CH.sub.3, C.sub.2 H.sub.5                            ##STR8##             M, n, as above.                                          ##STR9##             M, n, as above.                                          ##STR10##            M, n, as above.                                          ##STR11##            M, n, as above.                                         16. M[O.sub.3 P(CH.sub.2).sub.nC(SH)CH(SH)].sub.2 ;                                                 M, n, as above.                                          ##STR12##             M, n, as above, R = CH.sub.3, C.sub.2 H.sub.5,                               CH(CH.sub.3).sub.2 or                                                         C(CH.sub.3).sub.3. as in 1.                             18. M[O.sub.3 P(CH.sub.2).sub.n OPR.sub.2 ].sub.2 ;                                                 M, n and R as                                                                 in 1.                                                   19. M[O.sub.3 P(CH.sub.2).sub.nBR.sub.2 ].sub.2 ;                                                   M, n, and R as in                                                             1, or R = H.                                            20. M[O.sub.3 P(CF.sub.2).sub.nSO.sub.3 H].sub.2 ;                                                  M, n, as above.                                         21. Compounds above in which the P(CH.sub.2).sub.n linkage                    is replaced by a PO(CH.sub.2).sub.n link.                                     ______________________________________                                    

Compounds 1, 2, 4, 7, 8, 9, 10, 11, 12, 16, and 18 are useful ascomplexers for immobilization of catalytically active metals, such asPd⁺², Lr⁺¹, Rh⁺¹ Ru⁺², Os⁺².

Compounds 3, 4, 5, 6, 8, and 20 are useful as salt or ion exchangers.

Compound 13 is useful as an H₂ S scrubber.

Compounds 14 and 17 are useful sorbants.

Compound 15 is an electron transfer agent.

Compound 20, like the product in example 32, is useful as a solid acidcatalyst.

The oxy acids of phosphorous which are used as intermediates in thisexample are obtained by known processes such as those indicated inExample 34.

EXAMPLE 37

Using the method outlined in Example 1, the following compounds areprepared:

    ______________________________________                                         1.Zr(O.sub.3 PCH.sub.2 Cl).sub.2                                              2.Th(O.sub.3 PCH.sub.2 Cl).sub.2                                              3.Pb(O.sub.3 PCH.sub.2 Cl).sub.2                                              4.U(O.sub.3 PCH.sub.2 Cl).sub.2                                               5.Ti(O.sub.3 PCH.sub.2 Cl).sub.2                                              6.Zr(O.sub.3 PCH.sub.2 CH.sub.2 Cl).sub.2                                     ##STR13##                                                                     ##STR14##                                                                     ##STR15##                                                                     ##STR16##                                                                     ##STR17##                                                                     ##STR18##                                                                     ##STR19##                                                                    14.Zr(O.sub.3 POCH.sub.2 CH.sub.2 CN).sub.2                                   15.Zr(O.sub.3 PCH.sub.2 SH).sub.2                                             16.Zr(O.sub.3 PCH.sub.2 CH.sub.2 COOH).sub.2                                  17.Th(O.sub.3 PCH.sub.2 CH.sub.2 COOH).sub.2                                  18.Zr(O.sub.3 PCH.sub.2 COOH).sub.2                                            ##STR20##                                                                    20.Zr(O.sub.3 PCH.sub.2 CH.sub.2 SO.sub.3 H).sub.2                            21.Zr(O.sub.3 PCH.sub.2 CH.sub.2 CH.sub.2 SO.sub.3 H).sub.2                   22.Ti(O.sub.3 PCH.sub.2 CH.sub.2 CH.sub.2 SO.sub.3 H).sub.2                   23.Zr(O.sub.3 PCH.sub.2).sub.2                                                 ##STR21##                                                                    25.Zr(O.sub.3 PCH.sub.2 CH.sub.2 SH).sub.2                                    26.Zr(O.sub.3 PCH.sub.2 CH.sub.2 Br).sub.2                                    27.Zr(O.sub.3 PCH.sub.2 CH.sub.2 NH.sub.2).sub.2                              28.Zr(O.sub.3 PCH.sub.2 CN).sub.2                                             29.Zr(O.sub.3 PCH.sub.2 CH.sub.2 CH.sub.2 COOH).sub.2                         30.Zr(O.sub.3 PCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 COOH).sub.2                31.ZrO.sub.3 PCH.sub.2 CH.sub.2 CH.sub.2 PO.sub.3                             32.Ti(O.sub.3 PCH.sub.3).sub.2                                                33.Th(O.sub.3 PCH.sub.3).sub.2                                                34.Zr(O.sub.3 PCH.sub.3).sub.2                                                35.Th[O.sub.3 P(CH.sub.2).sub.17 CH.sub.3 ].sub.2                              ##STR22##                                                                     ##STR23##                                                                    38.Zr(O.sub.3 PCH.sub.2 SCH.sub.2 CH.sub.3).sub.2                              ##STR24##                                                                    40.Zr(O.sub.3 PCH.sub.2 CHCH.sub.2).sub.2                                     41.ZrO.sub.3 P(C.sub.10 H.sub.20)PO.sub.3                                     42.Th(O.sub.3 PCH.sub.2 OH).sub.2                                              ##STR25##                                                                     ##STR26##                                                                     ##STR27##                                                                    46.Zr(O.sub.3 POH).sub.2/3 (O.sub.3 PCH.sub.2 CHCH.sub.2).sub.4/3             47.Zr[O.sub.3 P(C.sub.10 H.sub.20)PO.sub.3 ].sub.2/3 (O.sub.3 POH).sub.4/3    ______________________________________                                    

Compounds 7 and 10 are useful for absorbing organic compounds fromaqueous media.

Compounds 14, 15, 25 and 28 are useful for absorbing Cu⁺² and Ag⁺ fromaqueous solution.

Compounds 16, 18, 29 and 30 are useful for loading Cu⁺², Ni⁺², and Co⁺².

Compounds 20 and 21 are useful for loading Cu⁺².

What is claimed is:
 1. A process for the production of phosphoruscontaining organo substituted inorganic polymers which comprisesreacting in a liquid medium at least one organophosphorus acid compoundof the formula:

    [(HO).sub.2 OP].sub.n R

wherein n is 1 or 2 and R is an organo group covalently coupled tophosphorus and wherein when n is 2, R contains at least two carbon atomsand is directly or indirectly coupled to the phosphorus atoms throughdifferent carbon atoms whereby the two phosphorus atoms are separated byat least two carbon atoms, with at least one tetravalent metal ionselected from the group consisting of zirconium, cerium, thorium,uranium, titanium, lead and mixtures thereof to precipitate from theliquid medium, a solid inorganic polymer in which, in the solidinorganic polymer, the molar ratio of phosphorus to tetravalent metal isabout 2 to 1 and in which the organo group is covalently bonded tophosphorus and phosphorus is linked to the tetravalent metal throughoxygen.
 2. A process as claimed in claim 1 in which the liquid medium isa liquid medium in which the organo phosphorus acid compound is formed.3. A process as claimed in claim 1 in which the liquid medium is water.4. A process as claimed in claim 1 in which the molar ratio ofphosphorus to tetravalent metal ion in the liquid medium is in excess of2 to
 1. 5. A process as claimed in claim 1 in which there is present forreaction with the tetravalent metal ion an acid selected from the groupconsisting of phosphorous acid, phosphoric acid and mixtures thereof. 6.A process as claimed in claim 1 in which the formed inorganic polymer issemi-crystalline and in which the reactants are refluxed to increasecrystallinity of the inorganic polymer.
 7. A process as claimed in claim1 in which the reaction is carried out in the presence of a sequesteringagent for the tetravalent metal ion.
 8. A process as claimed in claim 6in which a sequestering agent for the tetravalent metal ion is presentduring formation of the inorganic polymer and reflux.
 9. A process asclaimed in claim 1 in which the reaction is carried out at a temperatureup to the boiling point of the liquid medium.
 10. A process as claimedin claim 1 in which the reaction is carried out at a temperature fromambient to about 150° C.
 11. A process as claimed in claim 1 in whichthe reaction is carried out at a temperature from ambient to about 100°C.
 12. A process as claimed in claim 1 in which the organophosphorusacid compound comprises an organo phosphonic acid.
 13. A process asclaimed in claim 1 in which the organophosphorus acid compound comprisesa monoester of phosphoric acid.
 14. A process for the production ofinorganic phosphonate polymers which comprises reacting in a liquidmedium at least one phosphonic acid compound of the formula:

    [(HO).sub.2 OP].sub.n R

wherein n is 1 or 2 and R is an organo group covalently coupled tophosphorus through carbon and wherein when n is 2, R contains at leasttwo carbon atoms and each phosphorus is coupled to different carbonatoms, with at least one tetravalent metal ion selected from the groupconsisting of zirconium, cerium, thorium, uranium, titanium, lead andmixtures thereof to precipitate from the liquid medium, a solidinorganic phosphonate polymer in which, in the solid inorganicphosphonate polymer, the molar ratio of phosphorus to tetravalent metalis about 2 to 1 and in which the organo group is covalently bonded tophosphorus through carbon and phosphorus is linked to the tetravalentmetal through oxygen.
 15. A process as claimed in claim 14 in which theliquid medium is a liquid medium in which the phosphonic acid compoundis formed.
 16. A process as claimed in claim 14 in which the liquidmedium is water.
 17. A process as claimed in claim 14 in which the molarratio of phosphorus to tetravalent metal ion in the liquid medium is inexcess of 2 to
 1. 18. A process as claimed in claim 14 in which there ispresent for reaction with the tetravalent metal ion an acid selectedfrom the group consisting of phosphorous acid, phosphoric acid andmixtures thereof.
 19. A process as claimed in claim 14 in which theformed inorganic phosphonate polymer is semi-crystalline and in whichthe reactants are refluxed to increase crystallinity of the inorganicpolymers.
 20. A process as claimed in claim 14 in which the reaction iscarried out in the presence of a sequestering agent for the tetravalentmetal ion.
 21. A process as claimed in claim 19 in which a sequesteringagent for the tetravalent metal ion is present during formation of theinorganic phosphonate polymer and reflux.
 22. A process as claimed inclaim 14 in which the reaction is carried out at a temperature up to theboiling point of the liquid medium.
 23. A process as claimed in claim 14in which the reaction is carried out at a temperature from ambient toabout 150° C.
 24. A process as claimed in claim 14 in which the reactionis carried out at a temperature from ambient to about 100° C. 25.Inorganic organophosphonate polymers prepared by the process of claim14.
 26. A process for the production of phosphorous containing organosubstituted inorganic polymers which comprises reacting in a liquidmedium at least one monoester of phosphoric acid having the formula:

    [(HO).sub.2 OP].sub.n R

wherein n is 1 or 2 and R is an organo group covalently coupled tophosphorous through an oxygen and wherein when n is 2, R contains atleast two carbon atoms and each phosphorous is coupled through oxygen todifferent carbon atoms, with at least one tetravalent metal ion selectedfrom the group consisting of zirconium, cerium, thorium, uranium,titanium, lead and mixtures thereof to precipitate from the liquidmedium, a solid inorganic polymer in which, in the solid inorganicpolymer, the molar ratio of phosphorous to tetravalent metal is about 2to 1, the organo group is covalently bonded to phosphorous through anoxygen and phosphorous is linked to the tetravalent metal throughoxygen.
 27. A process as claimed in claim 26 in which the liquid mediumis a liquid medium in which the monoester of phosphoric acid is formed.28. A process as claimed in claim 26 in which the liquid medium iswater.
 29. A process as claimed in claim 26 in which the molar ratio ofphosphorous to tetravalent metal ion in the liquid medium is in excessof 2 to
 1. 30. A process as claimed in claim 25 in which there ispresent for reaction with the tetravalent metal ion an acid selectedfrom the group consisting of phosphorous acid, phosphoric acid andmixtures thereof.
 31. A process as claimed in claim 25 in which theformed inorganic polymer is semi-crystalline and in which the reactantsare refluxed to increased crystallinity of the inorganic polymer.
 32. Aprocess as claimed in claim 25 in which the reaction is carried out inthe presence of a sequestering agent for the tetravalent metal ion. 33.A process as claimed in claim 31 in which a sequestering agent for thetetravalent metal ion is present during formation of the inorganicpolymer and reflux.
 34. A process as claimed in claim 25 in which thereaction is carried out at a temperature up to the boiling point of theliquid medium.
 35. A process as claimed in claim 25 in which thereaction is carried out at a temperature from ambient to about 150° C.36. A process as claimed in claim 25 in which the reaction is carriedout at a temperature from ambient to about 100° C.
 37. A process for theproduction of phosphorous containing organo substituted inorganicpolymers which comprises reacting in a liquid medium at least onemonoester of phosphoric acid having the formula:

    (HO).sub.2 OPR

wherein R is an organo group covalently coupled to phosphorous throughcarbon with at least one tetravalent metal ion selected from the groupconsisting of zirconium, cerium, thorium, uranium, titanium, lead andmixtures thereof to precipitate, from the liquid medium, a solidinorganic polymer in which, in the solid inorganic polymer, the molarratio of phosphorous to tetravalent metal is about 2 to 1, the organogroup is covalently bonded to phosphorous through an oxygen andphosphorous is linked to the tetravalent metal through oxygen.